The Solubility of Aniline Hydrochloride in Water

dichlorosilane) of white solids melting at 238-244" was ob- tained by filtration. The crude product was recrystallized three times from a mixture of b...
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melt which became clear liquid a t about 320'. It was believed to be impure hexaphenyldisilane. The benzene extract was concentrated to about 10 ml., and to this On was added 20 ml. of petroleum ether (b.p. 60-70'). cooling to room temperature 2.2 g. (53% based on diphenyldichlorosilane) of white solids melting at 238-244" was obtained by filtration. The crude product was recrystallized three times from a mixture of benzene and ethanol t o give 1.2 g. (29%) of colorless needles melting a t 260-262" to form a somewhat gelatinous mass which became water-clear liquid a t 266' (uncor.). A w l . Calcd. for CiH&i3: Si, 12.00. Found: Si, 11.98, 11.84. Three check runs were made. In two of these runs a product melting at 302-303' was isolated. Analysis showed that it, too, had the composition of octaphenyltrisilane. From molecular model studies we suspected that this inconsistency in the melting points of these two products might possibly be due to the existence of isomeric forms. Further studies arc now in progress. Pentaphenylch1orodisilane.-A triphenylsilylpotassium suspension prepared according to the procedure described above was added fairly rapidly to 4 g. (0.016 mole) of diphenyldichlorosilane dissolved in 20 ml. of ether. It was noticed that the Erst few dropsof triphenylsilylpotassium was decolorized immediately when it was added to the diphenyldichlorosilane solution. When addition was completed, a gray suspension was formed. Color Test Ill immediately after the addition was negative. The mixture was stirred 1 hour a t room temperature and was filtered by suction. The solvent was distilled from the filtrate to give 7.1 g. of colorless solids melting a t 120-140'. The crude product was recrystallized twice from petroleum ether (b.p. 6C-70") to give colorless granular crystals melting a t 154-155" (uncor.). The yield of pure product was 3.7 g. (50%). Anal. Calcd. for CNHZ5Si2C1:Si, 11.79; C1, 7.43. Found: Si, 11.76, 11.81; C1, 7.42, 7.36. Pentaphenylchlorodisilane is an interesting compound because even though it can be hydrolyzed in aqueous basic solution t o give the corresponding hydroxy compound, still, unlike the triphenylchlorosilane, it is quite stable in air. A sample of this compound was put in a vial loosely plugged with cotton. After 3 months there was no depression in its melting point. Its preparation has been checked several times. From some preliminary work it was found that pentaphenylchlorodisilane can be treated with sodium in boiling xylene t o give a white solid, presumably decaphenyltetrasilane. Further work is now in progress. DEPARTMENT OF CHEMISTRY IOWA STATE COLLEGE AMES,IOWA RECEIVED AUGUST 24, 1951

Phenylphosphine' BY ROBERTJ, HORVAT AND ARTHURFURST

Phenylphosphine has been previously prepared by reducing dichlorophenylphosphine directly with anhydrous hydrogen iodideI2p3or by .first converting the dichlorophenylphosphine to diiodophenylphosphine hydrogen iodide and treating this with absolute alcoh01.~ Yields were increased only after many hours of reaction. It is possible to obtain phenylphosphine in much shorter time and in comparable over-all yields by simply reducing the dichlorophenylphosphine with lithium aluminum hydride. Experimental To an ice-cold solution of 4.18 g. (0.11 mole) of lithium alliminum hydride in 200 ml. of absolute ether was added (1) A grant-in-aid from Research Corporation is gratefully acknortledged; also the technical assistance of 0. Clark Chisim. ( 9 ) A. Michaelis, Ber., 1, 6 (1874). (3) &. Lecoq, B d l . soc. chim. Bell., 4S, 199 (1935). (4) 8.kohfer End A. Michaelis, Bcr., 10, 807 (1877).

drop by drop 35.5 g. (0.2 mole) of dichlorophenylphosphine (Victor Chemical Works) dissolved in 200 ml. of absolute ether. The reaction mixture turned yellow and soon began to reflux. After the addition was complete the mixture was refluxed for one hour, cooled and filtered through glass wool. In an atmosphere of nitrogen the ether was first removed; then the phenylphosphineo was distilled and collected as a colorless liquid a t 160-161 . The yield was 5.6 g. (25.4%); hydrogen iodide salt, m.p. 136' (uncor.). DEPARTMENTS OF CHEMISTRY ST. MARY'SCOLLEGE AND UNIVERSITY OF SAN FRANCISCO SANFRANCISCO 17, CALIFORNIA RECEIVED SEPTEMBER 24, 1951

The Solubility of Aniline Hydrochloride in Water BY EDWARD H . HOUSEAND

JOHN

H. WOLFENDEN

Three values for the solubility of aniline hydrochloride are recorded in the literature and regularly quoted in works of reference. Two of these relate to 25' and are in fair agreement; a t this temperature C. J. Peddle and W. E. S. Turner' report that 100 g. of water dissolves 107.1 g. of the salt while N. V. Sidgwick, P. Pickford and B. H. Wilsdonz report that 100 g. of the saturated solution contains 52.1 g. of the salt. The third solubility determination relates to 15', at which temperature S. v. Niementowski and J. v. Roszkowski3 report that 100 cc. of water dissolves 17.762 g. of aniline hydrochloride. This last figure is a t variance with common observation in the purification of the salt by recrystallization, and suggests a remarkably high temperature coefficient of solubility. The molal heat of solution computed from the recorded solubilities a t 15' and 25' implies an absorption of about 29 kcal. of heat, a value much larger than the value of 2.7 kcal. measured by Lo~guinine,~ than the heats of solution of other amine hydrochlorides, which commonly range between 1 and 4 kcal. per mole, and than the heat of fusion of the salt as deduced from the cryoscopic data of Leopoldj (cu. 2 kcal. per mole). The paucity of information about the solubility of this common organic compound and the implausibility of the only determination at any temperature other than 25' prompted us to measure the solubility over the temperature range from 0" to 100'. Saturated solutions of the pure recrystallized salt in water containing 0.2Q/, of aniline to repress hydrolysis were analyzed by titration with TABLE I SOLUBILITY OF ANILINEHYDROCHLORIDE Temp., "C.

&/IO0 g. HIO

Mole fraction

0 15 25 40 100

63.50 88.36 107.35 143.7 396

0.08112 .lo94 .1299

.1665 .355

(1) C. J. Peddle and W. E. S. Turner, J . Chcm. SOL.,103, 1202 (1913). (2) N.V. Sidgwick, P. Pickford and B. H.Wilsdon, ibid., 99, 1122 (1911). (3) S. v. Niementowski and 5. v. Roszkowski, 2. physik. Chem., IS, 145 (1897). (4) Cited by M. Berthelot, Ann. chim. Phys., Be. set., P i , 355 (1880). (6) G. H. Leopold, Z . physik. Chcm., 11, 58 (1910).

NOTES

Jan. 20, 1952

563

reaction mixtures in one of which the reaction has been proceeding for a time 7 longer than in the other, the value of the “optical density,” D’, of the less transparent sample compared with the more transparent sample is the value of the desired ( D t - Dt+.). A plot of logarithm D’vs. t will be a straight line of slope -k. As was true in the conventional Guggenheim method, the time interval T should be several times as great as the half-time of the reaction in order to obtain optimum precision. The above considerations indicate a method for determination of the rate constant of a first order corresponding to a heat of solution of 3.04 kcal. per mole, may be relied upon to give the solubility reaction in which the extinction of a reacting of aniline hydrochloride in water to within 0.7% system is measured against that of an identical over the temperature range 0’ to 50’ and to within mixture a t a different stage of the same reaction. 2.5% over the range 50’ to 100’. It will be noted This method has advantages compared to the that the previously accepted solubility a t 15’ is conventional Guggenheim method applied to a spectral study in which a solvent “blank” is used almost exactly one-fifth of the emended value. in that fewer readings must be taken for the same DEPARTMENT OF CHEMISTRY number of points, the readings extend over a shorter DARTMOUTH COLLEGE OCTOBER 4, 1951 time interval, and the readings need not be taken HANOVER, NEWHAMPSHIRE RECEIVED a t planned time intervals. The somewhat larger slit widths which are required because of the abThe Spectrophotometric Determination of the sorption of the “blank” are a disadvantage in the study of reactions in which the rate of change of Rate Constant of First Order Reactions’ e values for reactant and/or product with changing BY EDWARD L. KING wave length is large. The optical density of a solution in which the DEPARTMENT OF CHEMISTRY UNIVERSITY OF WIsCONSIN change A + B is occurring is given by the equation

standard alkali using brom thymol blue as indicator. Measurements were carried out a t O’, 15’) 25’, 40’ and, with reduced accuracy, a t 100’. At least six determinations were carried out a t each temperature. The best value for the solubility a t each temperature is summarized in Table I. The logarithm of the mole fraction N plotted against the reciprocal of the absolute temperature T gives a close approximation to a straight line. The equation

MADISON, WISCONSIN

Dt = logIa/I = 1 { u ( A ) t -k a ( B ) t )

where I is the cell length in cm., BA and BB are the molar extinction coefficients of A and B and (A)t and (B)t are the molar concentrations a t time t. If the rate law for this change is d(A)/dt = -k(A), the dependence of D upon t is given by equation 1

- €B) e - k f

RECEIVED AUGUST29, 1951

Sodium Perborate as a Reagent in Organic Chemistry. I. Preparation of Azo-Compounds BY S. M. MEHTAAND M. V. VAKILWALA

Sodium perborate has received little or no attention as a reagent for organic oxidations. Serantes’ and thus a plot of the logarithm of the quantity found it to be satisfactory for the oxidation of on the left side of the equation versus time will benzoic acid. Allen and Clark2 used it as a satisgive a straight line of slope -k. To make such a factory substitute for sodium peroxide in many plot, however, requires knowledge of the quantities oxidation reactions and described its action on a(A)o and B B . In a modification of the method diketones. A study of sodium perborate as a suggested by Guggenheim,2 the rate constant may reagent for the oxidation of organic compounds is be obtained without knowledge of either of these underway in this Laboratory. The present paper two quantities. describes the oxidation of aniline and a number of Equation 2 relates the optical densities of the its para-substitution products with sodium persolution a t times t and t 7 borate in acetic acid as a solvent. - E B ) e--kt (2) (Dt - D t + r ) = I(A)o (1 In glacial acetic acid the corresponding azoand it is seen that a plot of logarithm ( D t - Dt+.) compound may be obtained in relatively pure versus time would give a straight line of slope k form and, with the exception of aniline and 9if 7 is a constant time interval. In the usual anisidine, relatively free of tarry by-products. procedure readings of the optical density of the The yield of azo-compound varies with the temreaction mixture versus a solvent “blank” would be perature of reaction and with the concentration , tu, tl 7, t 2 7, and of the acetic acid. Maximum yields are obtained made a t times: t ~tz, in glacial acetic acid and at temperatures of ret, T. In view of the relationship action between 40 to 50’ (Table I). Addition of water to the acetic acid solvent markedly lowers the yield of oxidation product. a convenient means of determining the first order The product of the action of sodium perborate on rate constant is available. If in the two cells in aniline cannot be recovered by direct crystallizathe usual arrangement for spectrophotometric tion but must be removed from the reaction mixmeasurements, there are placed two identical (1) M. T.Serantes, Reo. farm., 66, No. 4 (1923); Analrs asoc. purm. (Dt/l(A)o

- EB]

= (€A

(1)

+

-

+

. . a ,

+

+

(1) This work was supported by a grant from the U. S. Atomic Energy Commission. (21 E. A. Guggenheim, Phil. Mag., 171 1, 538 (lQ26).

argenlina, 12, 58 (1923); C. A , , IS, 1134 (1926). (2) C. F. H. Allen and J. H . Clark, J . Chcm. Education, 19, 72 (1942).